Abstract
π-Conjugated polymers (CPs) have broad applications in high-performance optoelectronics, energy storage, sensors and biomedicine. However, developing green and efficient methods to precisely synthesize alternating CP structures on a large scale remains challenging and critical for their industrialization. Here a room-temperature, scalable and homogeneous Suzuki–Miyaura-type polymerization reaction is developed with broad generality validated for 24 CPs including donor–donor, donor–acceptor and acceptor–acceptor connectivities, yielding device-quality polymers with high molecular masses. Furthermore, the polymerization protocol significantly reduces homocoupling structural defects, yielding more structurally regular and higher-performance electronic materials and optoelectronic devices than conventional thermally activated polymerizations. Experimental and theoretical studies reveal that a borate transmetalation process plays a key role in suppressing protodeboronation, which is critical for large-scale structural regularity. Thus, these results provide a general polymerization tool for the scalable production of device-quality CPs with alternating structural regularity.
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All relevant data supporting the findings of this study are available in the Article and its Supplementary Information. Synthesis procedures and characterization for all the new compounds, computational studies and all copies of NMR spectra and gel permeation chromatography traces are available in the Supplementary Information. Source data are provided with this paper.
Change history
05 February 2024
A Correction to this paper has been published: https://doi.org/10.1038/s41563-024-01824-0
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Acknowledgements
We acknowledge financial support from the NSFC (51925306 (H.H.), 52222309 (Q.S.) and 52173187 (Q.S.)), National Key R&D Program of China (2018FYA 0305800 (H.H.)), Key Research Program of the Chinese Academy of Sciences (XDPB08-2 (H.H.)), China Postdoctoral Science Foundation (2021M703158 (H.X.)) and Fundamental Research Funds for the Central University. T.J.M. thanks the National Science Foundation Materials Research Science and Engineering Center at Northwestern University (DMR-2308691) and the Air Force Office of Scientific Research (FA9550-22-1-0423) for support. We thank X. Hao and J. Qiao from Shandong University for the exciton diffusion length measurements.
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H.H. directed the investigations and provided overall supervision. H.X. designed the experiments. H.X., W.X., X.Z. and Q.S. performed the synthesis experiments. Q.L. and D.Z. performed the device fabrications. Y. Lu, S.W. and Z.W. performed the DFT calculations. Y. Li and Y. Lin performed the trap density measurements. S.W., C.L. and X.Z. performed the atomic force microscopy and GIWAXS measurements. H.X., Q.S., T.J.M. and H.H. prepared the manuscript.
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Xiong, H., Lin, Q., Lu, Y. et al. General room-temperature Suzuki–Miyaura polymerization for organic electronics. Nat. Mater. 23, 695–702 (2024). https://doi.org/10.1038/s41563-023-01794-9
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DOI: https://doi.org/10.1038/s41563-023-01794-9
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